MX2010006032A - Additive for hydroconversion process and method for making and using same. - Google Patents

Abstract

The invention relates to an additive for hydroconversion processes, which is a solid organic material having a particle size of between about 0.1 and about 2,000 µm, an apparent density of between about 500 and about 2,000 kg / m3, a density skeletal between approximately 1,000 and approximately 2,000 kg / m3 and a humidity between 0 and approximately 5% p. Methods for the preparation and use of the additive are also provided. By using the additive of the present invention, the hydroconversion process can be performed with a high level of conversion.

Description

ADDITIVE FOR HYDROCONVERSION PROCESS AND METHOD FOR PREPARATION AND USE OF THE SAME BACKGROUND OF THE INVENTION The invention relates to an additive used in catalytic processes for hydroconversion.

Hydroconversion processes are known in general and an example of such a process is disclosed in co-pending United States patent application 12 / 113,305 filed May 1, 2008. process disclosed therein, the catalysts are provided in aqueous or other solutions, one or more catalytic emulsions (aqueous solution) in oil are prepared in advance, the emulsions are then mixed with the feedstock and the mixture is exposed to hydroconversion conditions.

The disclosed process is generally effective for the desired conversion. It should be noted, however, that the catalysts used are potentially expensive. It would be beneficial to find a way to recover this catalyst to reuse it.

Additionally, the formation of foam and the like in hydroconversion reactors can cause numerous undesired consequences and it would be desirable to provide a solution for such problems.

Hydroconversion processes in general for heavy waste, with high content of metal, sulfur and asphaltene, can not achieve high conversion rates (more than 80% p) without recycling and high concentration of catalyst.

The additives that are normally used to try to control the foam in the reactors can be expensive and can be decomposed chemically in the reaction zone, potentially leading to more difficult processing of derivative products and the like.

The invention According to the invention, an additive used in the catalytic hydroconversion processes is provided where the additive captures or adsorbs the catalytic metals and also native metals from the feedstock and concentrates them in a heavy stream or in a waste material without convert that leaves the process reactor, and this heavy current can be treated to recover the metals. The stream can be processed to obtain flake-like materials. These flakes can then be processed further to recover the catalytic metals and other metals in the flakes that are donated from the feedstock. This advantageously allows the metals to be used again in the process, or otherwise advantageously arranged.

The hydroconversion process comprises the steps of feeding a heavy load containing vanadium and / or nickel, a catalytic emulsion containing at least one metal of group 8-10 and at least one metal of group 6, hydrogen, a sulfurizing agent and a organic additive in a hydroconversion zone under hydroconversion conditions to produce an improved hydrocarbon product and a solid carbonaceous material containing said group 8-10 metal, said group 6 metal, and said vanadium.

In addition, the additive can be used to control and improve the overall fluid dynamics in the reactor. This is due to an anti-foaming effect caused by the use of the additive in the reactor, and said control of the foam can also provide improved control of the temperature in the process.

The additive is preferably an organic additive, and can preferably be selected from the group consisting of coke, carbon blacks, activated coke, soot and combinations thereof. Preferred sources of coke include, but are not limited to, coke from coals, and coke produced from hydrogenation or carbon rejection of virgin waste and the like.

The additive can be advantageously used in a process for liquid phase hydroconversion of fillers or feedstocks such as heavy fractions having an initial boiling point of about 500 ° C, a typical example of this being a vacuum residue.

In the hydroconversion process, the feed charge is contacted in the reaction zone with hydrogen, one or more ultradispersed catalysts, a sulfurizing agent and the organic additive. While the present additive would be suitable in other applications, a preferred process is performed in a three-phase upflow cocurrent flow bubbling column reactor. In this preparation, the organic additive can be introduced into the process in an amount between about 0.5 and about 5.0% p with respect to the feedstock, and preferably with a particle size between about 0.1 and about 2000 pm.

By carrying out the process as described herein using the organic additive of the invention, the organic additive captures or adsorbs the catalytic metals of the process, for example including the nickel and molybdenum catalytic metals, and also traps the metals in the feedstock. , being a typical example of this, vanadium. Therefore, the process product includes a significantly improved hydrocarbon product and unconverted waste which contain the metals. These unconverted wastes can be processed to obtain solids, for example flake-like materials, containing heavy hydrocarbon, organic additive and catalyst concentrate metals, and feedstock. These leaflets constitute a valuable source of metals for recovery as indicated above.

BRIEF DESCRIPTION OF THE DRAWINGS A detailed description of the preferred embodiments of the invention follows, with reference to the accompanying drawings, in which: Figure 1 illustrates schematically a process according to the invention; Y Figure 2 schematically illustrates a method for the preparation of an organic additive according to the invention; Y Figures 3a and 3b schematically illustrate the benefit of using the additive according to the invention; Figure 4 schematically illustrates the internal temperature profiles of the reactor when the additive of the invention is used; Figure 5 illustrates schematically the differential pressure profiles of the reactor in relation to the control of fluid dynamics when the additive of the invention is used; Figure 6 illustrates schematically the differential pressure profiles of the reactor in relation to the phase distribution when the additive of the invention is used.

Detailed description The invention relates to an additive used in the processes of catalytic hydroconversion of a heavy feed load. The additive acts as a captor or adsorber of the catalytic and native metals of the charge and concentrates them in a residual phase for a subsequent extraction. Additionally, the additive serves as a foam controlling agent and can be used to improve the general conditions of the process.

A brief description of this hydroconversion process is presented here, using unit 200 in Figure 1. In this hydroconversion process, the feed charge, which contains vanadium and / or nickel, is contacted with a catalyst consisting of one, two or more emulsions (water in oil) containing at least one metal of group 8-10 and at least one metal of group 6, under hydroconversion conditions, which means high partial pressure of hydrogen and high temperatures, and also in the presence of an additive that has the purpose of concentrating metals on its surface, making the process of metal recovery easier.

Within unit 200 the feed charge conversion occurs, and the flows or effluents of unit 200 include a product stream that includes an improved hydrocarbon phase, which can be separated into liquid and gaseous phases for further treatment and / or feeding to a gas recovery unit as desired, and a waste containing the additive that can be solidified or separated into a stream rich in solids, to be fed to a metal recovery unit, and vacuum residue without converting, that can be recycled The feedstock for the hydroconversion process can be any heavy hydrocarbon, and a particularly good feedstock is a vacuum residue which can have properties as those set forth in Table 1 below: Table 1 Alternative feeds include, but are not limited to, feeds derived from bituminous sands or impregnated with pitch and / or tar.

For a vacuum residue feed (RV), this can come from a vacuum distillation unit (UDV) for example, or from any other appropriate source. Other similar feeds can be used, especially if they are of a type that can be usefully refined through hydroconversion and contain feedstock metals such as vanadium and / or nickel.

As indicated above, the additive is preferably an organic additive such as coke, carbon black, activated coke, soot and a combination of them. These materials can be easily obtained from different sources at a very low cost. The organic additive may preferably have a particle size of between about 0.1 and about 2000 p.m.

The catalysts used are preferably a metallic phase as described in co-pending US Pat. No. 12 / 113,305. The metal phase is advantageously provided as a metal selected from groups 8, 9 or 10 of the periodic table of elements, and another metal selected from group 6 of the periodic table of elements. These metals can also be mentioned as group metals VIA and VINA, or metals group VIB and group VII IB according to previous versions of the periodic table.

The catalytic precursor metals of each class are advantageously prepared in different emulsions, and these emulsions are useful as feed, separated or together, for a reaction zone with a feed charge where the increase in temperature serves to decompose the emulsions and create a catalytic phase that disperses through the charge as desired. While these metals may be provided in a single emulsion or in different emulsions, both possibilities are within the scope of the present invention, it is particularly preferred to provide them in separate or different emulsions.

The metal (s) of group 8-10 can be advantageously nickel, cobalt, iron and combinations thereof, while the metal of group 6 can advantageously be molybdenum, tungsten and combinations thereof.

A particularly preferred combination of metals is nickel and molybdenum.

One embodiment of an appropriate hydroconversion process is that disclosed in a United States patent application filed concurrently with the record number of representative 09-289-2, which is incorporated herein by reference. In such a process, more than the two metals mentioned can be used. For example, two or more metals of group 8, 9 or 10 may be included in the catalytic phases or catalytic precursors of the emulsions.

The catalytic emulsion (s) and the heavy feedstock may be fed to the reactors preferably in amounts sufficient to provide a ratio between the catalyst metals and the heavy load, by weight, of between about 50 and about 1000 ppm by weight. Hydrogen can be fed into the process from any suitable source.

The reaction conditions can be as those set forth in Table 2 below: Table 2 According to the invention, then, in a mud or suspension type feeding system, the unit 200 receives a vacuum residue (RV). The particles of the additive can be added to the RV, in a concentration between 0.5-5% p with respect to the feed load, and agitated. The stirred suspension is preferably pumped at a high pressure, preferably higher than 200 barg, by means of pumps for high pressure mud. This sludge formed by the RV and additive mixture is also heated to an elevated temperature, preferably higher than 400 ° C. Upstream, the catalytic emulsions, sulfurizing agent and hydrogen are injected into the sludge feed. After the furnace that heats the sludge mixture, more hydrogen can be added if necessary.

The total mixture of RV, organic additive, catalytic emulsions, sulfurizing agent and hydrogen is introduced into the reactor and is hydroconverted deeply into the lighter materials desired. Most of the hydroconverted materials are separated as vapor in a high-pressure, high-temperature separator, and the vapor can be sent to a subsequent unit for hydrogenation and additional hydrocracking as needed.

Meanwhile, the bottom product of the separator, in the form of a heavy suspension liquid, can be sent to a vacuum distillation unit to recover, in vacuum, any remaining light material, and the remaining bottom residue remaining, which is the Unconverted waste can be sent to different types of processes where it can become a solid material.

The typical performance of a specific feed load is set forth in Table 3 below: Table 3 Power load Weight Residue of vacuum 100 Catalytic emulsions + 8 -. 8 - 10 Coke additive Washing oil (HGO) 2.6 - 3.6 Hydrogen 1.8- 3 One of the units for converting the bottom residue to a solid material could be a flake forming unit. The resulting flakes may advantageously have the following composition: Table 4 Physical state and arance Fragile solid API -5 - (- 14.4) Bright black color Volatility Negligible at room temperature Boiling point Greater than 500X Density at 15 ° C (kg / ma) 900- 1350 Insoluble in toluene% p 15-40 Asphaltenes (IP-143)% p 30-50 preferably 30-40 Insoluble in heptane (% p) 28-50 Carbon residue (Micron method)% p 22-55 Molybdenum ppm by weight 1500-5000 Vanadium ppm by weight 1400-6500 Nickel ppm by weight 50 - 3000 Carbon content% p 85-93 Hydrogen content% p 5-9 Carbon / hydrogen ratio 10-17 Total nitrogen% p 1.-2.5 Sulfur% p 2.2-2.7 Vacuum gas oil (%) 6-14 Ash% p 0.2-2.0 Volatile matter% p: 61.4 60-80 Heating power BTU / Lb 15700-16500 Moisture% p: 0 - 8.00 Hardness Index (HGI) 50-68 Softening point ° C: 110-175 Kinematic viscosity at 275 ° F cSt 13,000-15,500 Flash point ° C 300-310 Freezing point ° C 127 Simulated distillation (D-7169)% distillate (% p) T (° Q IBP 442. 9 1 445.6 5 490.7 10 510.9 15 527.0 20 541.9 25 557.7 30 574.9 40 618.9 50 668.5 58 715.0 These flakes, which contain the remaining organic additive and also the catalytic metals and the and / or the native metals of the feedstock that are captured by the additive according to the process of the present invention, can be provided to the consumers as a Useful source of metals, or can be used as fuel, or can be treated to extract metals for reuse as process catalysts, the like and other uses.

Of course, the metals to be recovered include not only the catalytic metals used in the process, but also certain metals such as vanadium that are native to the feedstock.

As stated above, an organic additive constitutes an important aspect of the hydroconversion process disclosed in the United States patent ication filed concurrently with record number 09-289-2. This additive can be obtained from numerous sources, for example coke from many sources including coals, carbon blacks, activated coke, soot from gasifiers, cokes produced from hydrogenation or carbon rejection reactions, virgin waste and the like. It should be noted that these numerous sources allow the preparation of the additive from readily available and accessible raw materials. A method for preparing the additive from said raw materials is indicated below, and the final result for use as an additive according to the invention, preferably has a particle size of between about 0.1 and about 2,000 μm, a bulk density between about 500 and about 2,000 kg / m 3, a skeletal density of between about 1,000 and about 2,000 kg / m 3 and a humidity of between 0 and about 5% p. More preferably, the particle size is between about 20 and about 1000 p.m.

With respect to Figure 2, a method for preparing the additive of the present invention is illustrated. The starting raw material may typically be as described above, and may have properties such as: bulk density of between about 500 and about 2000 kg / m3, a humidity of between about 5% and about 20% p, a hardness of between about 20 HGI and about 100 HGI and a maximum particle size between about 5 cm and about 10 cm. This raw material is preferably first fed to a primary milling station 61 where the material is milled to reduce the particle size by an order of magnitude approximately. These preliminarily milled particles can have a particle size typically between about 20 mm and about 20 μm, and are fed to a drying zone 62. In the drying zone, the particles are exposed to an air stream, which extracts the moisture of the particles preferably less than about 5% p. The resulting dry particles are then fed to a primary classification zone 63, where the particles are separated into a first group, which meets a desired particle size criterion, for example less than or equal to about 1000 pm, and a second group which does not meet this criterion. As shown, while the material with acceptable size particles of the first group is fed to a secondary sorting zone 66, the second group needs an additional milling and preferably is fed to a second milling station 64 where it is further comminuted or otherwise Mode is treated mechanically to reduce the particle size. The ground product additionally it is fed in another classification zone 65, where the particles that now meet the criteria are fed again to be combined with those that initially met the criteria, and those that do not yet meet the criteria are recycled again through a station secondary grinding 64 as necessary.

From the secondary sorting station 66, it will now be observed that part of the particulate material does not meet the desired criteria, and this material can be separated and fed to an agglomeration station 70, where the particles are granulated to obtain particles with a larger diameter by a mixture of chemical substances. Meanwhile, the particles meeting the criteria in station 66 are now fed to a thermal treatment station (67), where they are exposed to a stream of hot air to raise their temperature to between about 300 and 1000 ° C and, under In these conditions, a process of porogenesis occurs. The heated particles are then fed to a cooling station (68) where they are cooled, in this case with a stream of air cooled by water. The resulting particles should have a temperature below about 80 ° C.

The heated and cooled particles can now be fed to an additional classification zone 69, to again separate any particle that does not meet the desired particle size criterion. Said particles that do not pass can be fed to the agglomeration zone 70, while those that pass can be used as the additive according to the invention.

The organic additive can be used ideally in an amount between about 0.5 and about 5% p with respect to the charge of Feeding, and in this amount can serve both to capture or adsorb the catalyst metals and the feedstock and to control the foaming in the reactor to provide more stable and efficient conditions in the reactor.

In the reactor, when the additive of the present invention is used, the reaction can be advantageously carried out at a gas velocity greater than or equal to about 4 cm / s.

These advantageous process conditions can produce a hydroconversion with an asphaltene conversion rate of at least about 75% p and a Conradson carbon conversion rate of at least about 70% p, and these rates are difficult or impossible to obtain otherwise , using conventional techniques.

Observing in Figures 3a and 3b, two views of reactors of the hydroconversion process are shown. In Figure 3a, a reactor is shown where the process is being carried out without any additive according to the invention. As shown, the reaction is a biphasic reaction, and has a lower portion only with liquid and an upper portion, approximately 60-70% v, of foam and gas. Figure 3b shows a similar reactor when operating with the additive of the present invention, and shows that the foam is much better controlled in this case, with 70-80% v of the reactor filled with a liquid and solid phase, and a higher than 20-30% v of the gas-containing reactor.

This reduction of the foam occurs due to the breaking of bubbles, thereby decreasing diffusion problems by providing better contact between the gas and the liquid. These conditions, obtained using the additive according to the invention, lead to a much more efficient conversion, better control of temperature and a reduction of unwanted hot spots.

During the course of the hydroconversion reactions in unit 200, the heavier components of the feedstock tend to become insoluble in the light fractions generated by the reaction itself. The high temperatures stimulate the polymerization and condensation reactions of aromatic groups and when the difference between the solubility parameters of the two pseudo components (asphaltenes and maltenes) approaches a critical value, the system causes the appearance of sediments and consequently, the precipitation of asphaltenes and coke formation. This loss of stability of the residue at a very high conversion level can be controlled by the capture or adsorbent effect of coke and asphaltenes of the organic additive. Therefore, a maximum conversion can be achieved. This capture or adsorbent effect is shown in example 1.

EXAMPLE 1 Coke / asphaltene capture or adsorber capacity This example illustrates the ability of the carbonaceous additive to trap asphaltenes, coke and / or polycondensed aromatics.

In this example, petrozuata petroleum coke was used to generate the carbonaceous additive, this coke comes from a delayed coking process. This coke was thermally treated with air through a process of moderate combustion (porogenesis) to generate some porosity and surface area. The particle size was adjusted in the range of 200 - 900 μm, following the scheme shown in Figure 2, the carbonaceous additive was generated and the following experimentation was carried out.

Table 5 shows the composition of Petrozuata coke.

Table 5 10 g of vacuum residue (RV) Merey / Mesa were mixed with 100 ml of toluene; the mixture was placed under agitation to dissolve the RV. After that, 120 ml of n-heptane was added, stirring was maintained for 10 min. Then the carbonaceous additive in an amount of 1.5% p was added to the RV. Subsequently, it was stirred for 24 h. Finally, the sample was filtered, washed with n-heptane and the carbonaceous additive was dried in an oven for 4 h. After that, the cooled solid that was obtained was weighed. The amount of asphaltenes retained per gram of additive used was calculated according to the initial amount of additive used.

Table 6 shows the pore size, the surface area and the capacity of the carbonaceous additive to capture or adsorb asphaltenes.

Table 6 Pore size (Á) 15.6 Surface area (m2 / g) 270 Asphaltene capture capacity (% p) 13 EXAMPLE 2 Metal capture This example illustrates the ability of the carbonaceous additive to capture metals.

In this example, the flake-like material containing the unconverted vacuum residue and the remaining organic additive was used to quantify the metal content and the mass balance of metals of the hydroconversion process.

In this example the remaining organic additive was separated using a process of de-solidification with toluene as solvent. Following the scheme shown in Figure 1, the leaflets were generated and the following experiment was carried out. 50.00 g of flakes were dissolved in 350 ml of hot toluene, this mixture was then centrifuged at 1500 rpm for 20 minutes to separate the additive from the unconverted residue. The solids were decanted and washed using Soxhlet extraction with toluene, which is a continuous extraction method whereby the fresh solvent circulates continuously through the compound to be extracted. After that, the solids were dried in a vacuum oven for two hours at 130 ° C. The unconverted vacuum residue was recovered by evaporation of the toluene. In this example the amount of dry solids was 4.9 g.

Finally, the metal content in the solids and in the vacuum residue without converting by inductively coupled plasma (ICP) coupled to an OES optical detector was determined.

Table 7 shows the content of Mo, Ni and V in the flakes, the additive and the vacuum residue without converting.

Table 7 ?? Ni V Fe Analysis of leaflets (ppm in weight) 1977 1183 2103 459 Analysis of the dry solid additive (ppm by weight) 3812 2790 3984 822 Metal calculated in dry solids3 (ppm in weight) 1868 1367 1952 403 Relations15 of recovered metal (% p) 94. 5 115.6 9.8 87.8 Residue of vacuum without converting (ppm by weight) < 5.0 65 65 < 5.0 Conditions of the experiment Solvent Toluene Measured flakes (g) 10. 00 Measured dry solids (g) 4. 90 < a) Metals calculated in dry solids = Analysis of dry solids * Measured dry solids (g) / Measured flakes (g). () Some yields above 100% - within the experimental error.

EXAMPLE 3 Fluid dynamics and temperature control Following the scheme shown in Figure 1, the following experimentation was carried out.

The test was performed using a sample of vacuum residue (RV) of Canadian crude oil, prepared from Athabasca crude.

This RV was fed to a sludge-type bubble column reactor without internal components, with a total capacity of 10 BPD, with a temperature control based on a preheating and cold gas injection system. This reactor has a length of 1.6 m and a diameter of 12 cm.

For this test the reactor was used at 0.42 T / m3h. Three vertical slurry reactors connected in series were used during this test. The conditions were maintained for 1 1 days.

The conditions are summarized in Table 8.

Table 8 Feeding characteristics API Density (60 ° F) 2.04 Residue 500 ° C + (% p) 97.60 Asphaltenes (insoluble in heptane) (% p) 21.63 Metal content (V + Ni) (ppm by weight) 462 Sulfur (% p) 6.56 Process variables WSHV (T / m3h) 0.42 Feeding rate (kg / h) 24 Total pressure (barg) 169 Average reactor temperature (° C) 453 Gas / Liquid Ratio (scf / bbl) 34098 Gas surface velocity (first reactor inlet) (cm / s) 7.48 Particle size (pm) 200-300 Concentration of organic additive (% p) 1.5 Concentration of nickel catalyst (ppm by weight) 92 Molybdenum catalyst concentration (ppm by weight) 350 During this test the internal temperatures of the first reactor were measured in 12 different peaks, resulting in the profile shown in Figure 4.

In Figure 4 it is possible to observe the effect of the additive on the temperature. At the beginning of the test the profile varies between 2-4 ° C, in intervals of 10 hours, for the same peak, it presents an unstable behavior. After the additive reaches a stable concentration inside the reactor the profile varies, at most, less than 2 ° C and the behavior is significantly more stable.

The pressure differentials were measured for the three reactors, obtaining the profile shown in Figure 5.

This profile shows that around the point of the 100 hours of processing the three reactors have a stable concentration of solids, which is significant since the pressure differentials show an almost linear behavior from the first hour. This is in accordance with the temperature profile, which has a stable behavior from the same first hour.

This proves that the additive provides a fluid dynamic control, which also acts, at the same time, as a temperature control.

EXAMPLE 4 Foam control and phase distribution Following the scheme shown in Figure 1, the following experiment was carried out.

This example was carried out using a vacuum residue (RV) of Venezuelan crude, Merey / Mesa.

This RV was fed to a sludge-type bubble column reactor without internal components, with a total capacity of 10 BPD, with a temperature control based on a preheating and cold gas injection system.

For this test the reactor was used at 0.4 T / m3h (space velocity), using the vertical mud type reactors connected in series. The plant was in continuous operation for 21 days.

The conditions are summarized in Table 9.

Table 9 Characteristics of the power load API Density (60 ° F) 5. 0 Residue 500 ° C + (% p) 96. 3 Asphaltenes (IP-143) (% p) 19. 3 Metal content (V + Ni) (ppm by weight) 536 Sulfur (% p) 3. 28 Process variables WSHV (T / m3h) 0. 4 Feeding rate (kg / h) 24 Total pressure (barg) 170 Average reactor temperature (° C) 452. 1 Gas / Liquid Ratio (scf / bbl) 40738 Gas surface velocity (first reactor inlet) (cm / s) 6. 4 Particle size (μ ??) 212-850 Concentration of organic additive (% p) 1. 5 Concentration of nickel catalyst (ppm by weight) 132 Concentration of molybdenum catalyst (ppm by weight) 500 During the test, pressure differentials were measured in the three reactors, yielding the profile shown in Figure 6.

As this profile shows, the time to fill each reactor was approximately 15 hours, this is due to the time in which the pressure The reactor differential has a measure that is more likely to be stable. In this profile it can be seen that the first reactor reaches the stable measurement in about 15 hours and after the first reactor is completely filled, the second reactor takes around another 15 hours to reach the stable measurement, and the same behavior shows the third reactor.

After fully filling the reactors the total time for stabilization is around 75 hours.

The reduction of foam, due to the concentration of solids inside the reactors, is evidenced in the increase in pressure differentials, as a consequence of the increase in the amount of liquid.

With the pressure differentials it is possible to calculate the phase distribution for the first reactor. This differential was calculated under two conditions: 0 hours and during the test, as an average after the stabilization time (75 hours), the results are summarized in Table 10.

Table 10 Sin Sin Terms additive additive Hours in operation After 75 h 0 Temperature (° C) 380 449 ?? in the first reactor (mbar) 26. 5 59.85 Density of the liquid (kg / m3) 804. 6 760 Retention of liquid 0. 34 0.69 Gas retention 0. 66 0.28 Retention of solid 0 0.03 As shown in Table 10, the retention of liquid in the reactor, using the additive, increases by a factor of 2, which is related to a higher conversion because this increases the reaction volume.

The above examples demonstrate the excellent results obtained using the additive in the hydroconversion process according to the invention.

The present invention is provided in terms of details of a preferred embodiment. It should also be noted that this specific embodiment is provided for illustrative purposes and that the described embodiment is not to be construed in any way as limiting the scope of the present invention, which is defined instead by the claims set forth below.

Claims (30)

1. - Additive for hydroconversion processes comprising a solid organic material having a particle size of between about 0.1 and about 2,000 μ? T ?, a bulk density of between about 500 and about 2,000 kg / m3, a skeletal density of between about 1,000 and approximately 2,000 kg / m3 and a humidity of between 0 and approximately 5% p.

2. - Additive of claim 1, wherein the particle size is between about 20 and about 1,000 μm.

3. - Method for preparing an additive for a hydroconversion process comprising the steps of: feeding an unprocessed or raw carbonaceous material to a primary milling zone to produce a ground material having a reduced particle size with respect to the particle size of the carbonaceous material brutote heading; drying the ground material to produce a dry ground material having a moisture of less than about 5% p; feeding the dry milled material to a sorting zone to separate the particles that meet a desired particle size criterion from the particles that do not meet the desired particle size criterion; heating the particles that meet the desired particle size criteria to a temperature of between about 300 and about 1000 ° C; and cooling the particles leaving the heating step to a temperature of less than about 80 ° C to provide the additive.

4. - The method of claim 3, further comprising the steps of: feeding the particles that do not meet the desired particle size criteria to an additional milling step to provide an additional ground material; feeding the ground material additionally to an additional classification zone to separate additional particles that meet the desired particle size criterion of the particles that do not yet meet the desired particle size criterion; and recycling the particles that do not yet meet the desired particle size criteria to the additional classification zone.

5. - The method of claim 4, wherein the additional particles that meet the desired particle size criterion are added to the particles that met the desired particle size criterion before the heating step.

6. - The method of claim 3, wherein the heating step and the cooling step are carried out by exposing the particles to an air flow at a desired temperature.

7. - The method of claim 3, wherein the particles that meet the desired particle size criterion are fed to a secondary classification zone prior to the heating step, and wherein the secondary classification zone separates additional classified particles that comply with the desired particle size criterion, which are fed to the heating step, and particles that do not meet the desired particle size criterion are fed to an agglomeration station.

8. - Method of claim 3 further comprising the steps of: feeding the additive after the cooling step to a final classification zone, which separates the particles of the additive that comply with the desired particle size criterion of the additive particles that do not meet the desired particle size criterion, and feeding the additive particles that do not meet the desired particle size criterion to an agglomeration station.

9. - The method of claim 3, wherein the additive product comprises a solid organic material, having a particle size of between about 0.1 and about 2,000 pm, a bulk density of between about 500 and about 2,000 kg / m 3, a skeletal density between about 1,000 and about 2,000 kg / m3 and a humidity of between 0 and about 5% p.

10. - The method of claim 9, wherein the particle size is between about 20 and about 1,000 μm.

11. - Hydroconversion process comprising feeding a heavy feed charge containing at least one metal native to the charge selected from the group consisting of vanadium and nickel, a catalytic emulsion containing at least one metal from group 8-10 and at least one Group 6 metal, hydrogen and an organic additive to a hydroconversion zone under hydroconversion conditions to produce an improved hydrocarbon product and a solid carbonaceous material containing said group 8-10 metal, said group 6 metal and at least one metal native to the filler, wherein the organic additive comprises a solid organic material having a particle size of between about 0.1 and about 2,000 pm, a bulk density of between about 500 and about 2,000 kg / m 3, a skeletal density of between about 1,000 and about 2,000 kg / m 3 and a humidity of between 0 and about 5% p.

12. - Process of claim 11, wherein the organic additive is present in an amount of between about 0.5 and about 5% p with respect to the feedstock.

13. - Process of claim 11, wherein the process has a gas velocity greater than or equal to about 4 cm / s.

14. - Process of claim 11, wherein the hydroconversion exhibits an asphaltene conversion rate of at least about 75% p and a Conradson carbon conversion of at least about 70% p.

15. - Process of claim 11, wherein the heavy feed load is selected from the group consisting of vacuum residue, heavy crude, extra heavy crude and combinations thereof.

16. - Process of claim 11, wherein the heavy feed load is a vacuum residue.

17. - Process of claim 11, wherein the heavy feed load has an API gravity of between about 1 and about 7.

18. - Process of claim 11, wherein the heavy feed filler has a metal content of between about 200 and about 2,000 ppm by weight.

19. - Process of claim 11, wherein the metal content of the heavy feedstock comprises vanadium and nickel.

20. - Process of claim 1, wherein the catalytic emulsion comprises a first catalytic emulsion containing a metal of group 8-10 and a second catalytic emulsion containing a metal of group 6.

21. - Process of claim 11, wherein the metal of group 8-10 is selected from the group consisting of nickel, cobalt, iron and combinations thereof.

22. - Process of claim 11, wherein the group 6 metal is selected from the group consisting of molybdenum, tungsten and combinations thereof.

23. - Process of claim 11, wherein the metal of group 6 is in the form of a metal sulfide salt of group 6.

24. - Process of claim 11, wherein the organic additive comprises coke particles.

25. - Process of claim 11, wherein the process is carried out continuously.

26. - Process of claim 25, wherein the process is carried out with the feed in the form of a single step.

27. - Process of claim 11, wherein the hydroconversion conditions comprise a reactor pressure of between about 130 and about 210 barg and a reactor temperature of between about 430 and about 470 ° C.

28. - Process of claim 11, wherein the catalytic emulsion and the heavy feedstock are fed to the reactor in amounts to provide a ratio between the catalytic metals and the heavy feedstock, by weight, of between about 50 and about 1,000 ppm .

29. - Process of claim 11, wherein the yield of the product expressed in terms of weight, excluding the solid carbonaceous material, is greater than the weight of the heavy feed load.

30. - Process of claim 11, wherein the hydroconversion zone comprises a bubble column reactor in three-phase co-current upflow.